Organo-titanate reaction products and methods of preparing same



Patented June 8, I954 ATENT OFFICE ORGANO-TITANATE REACTION PRODUCTS ANDMETHODS OF PREPARING SAME Max Kronstein, New York, N. Y.

No Drawing. Application August 17, 1951, Serial No. 242,440

26 Claims. 1

This invention relates to organotitanate reaction products and methodsof making same, and has particular relation to reaction products ofsaturated aliphatic titanates or aromatic titanates with fatty acidesters of polyhydric alcohols or silicone resins.

The titanates have the formula Ti(OR)4, wherein R may be alkyl oraromatic, and are considered to be derivatives of TiCl4 or organicesters of a titanic acid. The alkyl titanates have been found to be oflimited practical value. They have been used in dilute solution aswater-repellants for fabrics, but their use as coating vehicles has beenlimited because of their poor film-forming characteristics.

One object of the present invention is to provide a process for reactingsaturated alkyl titanates with fatty acid esters of polyhydric alcoholsor with silicone resins, so as to produce uniform reaction productswhich may be obtained as products which are soluble in the usual coaltar solvents and which may be either softened by the addition ofplasticizers and oils, or hardened by combining with resinous compounds.

Another object is to provide such reaction products which are capable offorming a stable solution.

A further object is to produce such reaction products which can bemodified in appearance by the addition of coloring matter, combined withpaint pigments for use as coating materials, impregnating materials orpaints.

Another object is to produce such reaction products which may be appliedas coating or impregntaing compounds in the form of a solution orin afused form, and thereafter dried at about 100 C. to form insoluble,coherent film coatings, or which can be subjected to air drying toachieve film formation.

A further object is to produce such compounds which can be combined withoils, alkyd resins, phenolic resins, driers, plasticizers and theirsolutions, by either mixing or heating so as to produce novel coatingcompounds.

Still another object of the invention is to provide a method forproducing such reaction prodnets in gelled form, and may nevertheless beresolubilized into a soluble form by the method set forth in my Patent2,476,879, which discloses a process for resolubilizing oil gels byheating with metal soaps. These and other objects of the presentinvention will be better understood by reference to the followingexamples, which serve to illustrate the nature and utility of thepresent method and reaction products.

' In general, the present invention comprises a reaction product ofsaturated aliphatic or aromatic or alkyl aryl titanate and a fatty acidester of a polyhydric alcohol or a silicone resin, or both, saidcomponents being reacted in the presence of an organoperoxide at atemperature sufficient to effect the release of free oxygen in thereactants. One of the preferred polyhydric alcohols comprises linseedoil, one of the preferred silicone resins comprises methyl phenylsilicone, one of the preferred organoperoxides comprisesdi-tertiary-butyl peroxide, and one of the preferred organctitanatescomprises butyl titanate. Another preferred compound of the presentinvention comprises the reaction product of an organo titanatewith botha. fatty acid ester of a polyhydric alcohol and a silicone resin; forexample, butyl titanate, soyabean oil and methyl phenyl silicone,reacted in the presence of an organoperoxide such as di-tertiary-butylperoxide. The organoperoxide preferably comprises from about 1 to 25percent by weight of the non-volatiles. When fatty acid esters ofpolyhydric alcohols comprise the sole reactant with the organotitanate,the preferred amount of organoperoxide comprises from about 2.4 to 20percent by weight of the non-volatiles, and when silicone resinscomprise the sole reactant, about 1.6 to 13.5 percent by weight thereofis preferred. When the organetitanate is reacted with a mixture of fattyacid esters of polyhydric alcohols and silicone resins, about 6 to 23percent by weight thereof is preferred.

A reaction temperature range from about to 220 C. has been found to givesuperior results, although the organoperoxides generally release freeoxygen at temperatures from about 90 to C. Thereafter the reaction iscontinued to a temperature of about 220 C.

v The fatty acid esters of polyhydric alcohols used in this inventioncomprise esters of fatty acids having from 10 to 31 carbon atoms. IAmong the naturally occuring esters suitable for use are soybean oil,castor oil, linseed oil, China-wood oil, menhaden oil, isolene(synthetic dehydrated castor oil), lard oil, sperm oil, olive oil,sardine oil, saiiiower oil, candellila wax, carnauba wax and bees wax.Other esters include sorbitol esters of linseed oil fatty acids,ethylene glycol ricinoleate and ethylene glycol oleate. The fatty acidscontained in these acids have for example from 10 to 28 carbon atoms inthe sperm oil fatty acids, 25 to 31 carbon atoms in the bees wax fattyacids, 14 to 22 carbon atoms in the men-- haden and sardine oil fattyacids and 24 to 26 carbon atoms in'the carnauba wax acids.

The silicone resins employable in this invention comprise monovalenthydrocarbon poly-siloxane resins. By this term I mean poly-siloxaneresins having mono-functional or monovalent hydrocarbon radicals; i. e.one or more hydrocarbon radicals bonded each by a single bond to thesilicon atom. Among the poly-siloxane resins useful in thepresentinvention are methylyphenyl polysiloxane resin, ethylpoly-siloxane resin, cyclohexenyl poly-siloxane resin and vinylpolysiloxane resin. These poly-siloxane resins are:

referred to in the specification .by their common names, namely siliconeresins.

REACTION PRODUCTS OF ORGANOTITAN- ATES WITH FATTY ACID ESTERS OF'POLYHYDRIC ALCOHOLS- In the following examples, the oil and alkyltitanate were added together in the -presenceof the catalyst or prior'to the addition of the catalyst and/onin the presence of: volatiles.Heating was applied during the compoundingori thereafter. Gas formation,evidencing the release of free oxygen, was observedat'varying-intensities and at differenttemperatures and heatingratesdepending upon the type and amounts: of reactants employed; Theheating was continued .above gas formation: temperatures (9D:- 135 C.)to about 180 to 229* C. inaccordance with the increase. indegree of:viscosity desired;

Example 1 Example (a) were mixed with 3 additional parts of the samefree-oxygen releasing. catalyst. and were heated up to 160 C.-Itwasobservedthat no gelating occurred.

() The compoundproduced under. Example.

(1)) was modified by adding -l2 additional parts. ofthesame-oil and-8additional partsof. thesamei.

catalyst and heated to 175 C,- without gelationor solidification..The.resulting.compoundwas found to be. capablerof. gelation,. as shownin the. following Example'Z (c) (d) parts butyl .titanate were mixedwith parts linseed oil. (commercial grade 2-2 I and with 5 partst-butylperbenzoateand the mixture was heated under. stirring. At aroundto Y C. a reaction was observed anda uniform reddishoil was obtainedwhich darkened around C., at which point the escape of. white vapors wasobserved. At around C. a drop of thecompound on a glass plate had auniform clear appearance. Heating was discontinued around C. withoutgelation having occurred and 54 parts of the resulting oil was dissolvedin 65' g. benzol. A uniform solution was obtained which was applied toglass and sheetmetal and baked at 100 C., a continuous coating beingobtained.

(e) 16 parts butyl titanate were mixed with 43 parts China-wood oil andas a free oxygen releasing catalyst 6.5 parts t-butyl hydroperoxide wereadded. Upon heating, a heavy reaction occurred between 100 and 140 C.and a reddish uniform liquid was obtained, which was dissolved in 65parts toluene and was used as a coating material. The coatings driedtack free at room temperatures and upon'baking at around 110 C.

It should be noted that when China-wood oil is heated with a free-oxygenyielding catalyst in accordance with the method disclosed in my pendingapplication S. N. 33,676, filed June 1'7, 1948, now Patent 2,599,297,issued June 3, 1952, gelation or solidification occurs; whereas, withthe instant methodutilizing 'anziorganotitanate, gelation orsolidification may ice-avoided, although a quick drying, uniform coatingmaterial may be obtained with the instant method.

(1). 40. .partsbutyl titanate were mixed with eo parts dehydrated'castor oil and 6 parts ditertiary butyl peroxide. Stirring failed toproducerza'aclear-imixture, but upon heating, the resulting compound.became clear around 90 C. witlfa/slig'htly red color. Slight gasformation was observed above 105 C. Heating was continuediiuprto around170 0., at which point a drop of the compound on a glass plate gave aclear transparent layer. 74.5 .parts of therpro'dnot were obtained and:were'dissolved-in-a 2-11 ratioimmineralrspirits. and did: not. gel'onstanding. The product was dried at-109- C..into a veryhard filmin-theform of a coating;

(9) 20 parts of animal oil, light nienhaden fish: oil, were mixed with.7 parts butyl titanate and a mixture of 2 parts t.-butyl hydroperoxideand ()Jpart di-tertiary. butyLpei-oxide. On heating, -a very .strong*reactiorr-occurred around 100 and 136- 0. Heating. was-continued toabout C: A clearly solubleproduct-was:obtained (one part disselved in0.8 part-VIViP naphtha).

(77 15rparts -ofitetracyclohexyltitanate were mixed with 15 partsChina-wood .oil-and:2 parts t-butylperbenzoate. were. added." Themixture was heatedslowly. .Atabout and above 130 C;, a dark uniform oilwas. formed under slow gas development. Heatingtwas continued to andabove 209 C. for. about ten minutes. Three gramssubstance had i escaped.and the compound was dis-- solvedllzl.) inxylene. Theresulting clear andstable: solution. did not: showprecipitation orrgellin'gupon.standing-imaiglass container. for-.24

hours. .When coated on asteelpanel in 50-minutes at 1(103TC.,acoherent-film was obtained..-

(i) 31 parts of a commercial chemically isomerized. synthetic oil.iisolene oil, a dehydrated castor oil. .of.-the :WoburnChemica-l Co.)were mixed.with.5.5 parts-ofs-buty-l titanate and 5.5 partsof.tetracyclohexylrtitanate. 4 parts of a 1- hydroxy cyclo.- hexyl.-hydroperoxide -1 were added and atv room temperature no homogeneousmixture was obtainable. On heating, a clear, somewhat.- reddish,uniform-.mass was obtained above. 100 C..andaround 120? C. A drop spreadover a cool..glass. plate formed a uniform transparent viscous layer..Heating was continued up around 150 C.

One part of..the..product was dissolved (1:1) in xylene and a clearandstablesolution was obtamed. This solution. was clearlymiscible (1 partby volume .to 1 part by volume) with Chinawood oil; 0.5% of. a .driersolutioncobalt naphthenate liquid 161%. Co), was added and. when coatedona glass plate aclear transparent layer was obtained. Onheating thislayer at 100 C., a wrinkle finish. wasobtained which was comparable to.other China-wood oil basecoating compounds.-

(k) 20 parts-soybeanoil were mixed with 10 parts tetracyclohexyltitanate. and 1.5'parts pchlorobenzoyl peroxide was added. This mixturewas heated gradually under slight gas formation up to C; and a.darkbrown oil was obtained. Thisoil was clearly soluble (1 part. to

3 parts) in heavy mineral oil. This solution was clearly miscible in theproportion 2:1 with a resinous oil and clear stable solutions wereobtainable therewith.

(Z) parts butyl titanate and 10 parts lard oil, a non drying animal oil,were mixed with 5 parts xylol and 2 parts Uniperox 60 (a commercialliquid organic hydroperoxide in about (SO/65% solution with alcohols andketones of about the same boiling range as admixture and composed mainlyof cyclic hydrocarbon hydroperoxides containing six to eight carbonatoms and having an empirical formula C'IHBOOII) were added. Strongreaction began at 110 C. and continued up to about 170 C. Heating wasdiscontinued at 190 C. and a reddish oil was obtained. 7 g. volatilematter had evaporated.

The new compound was soluble (1:1) in Dekalin (decahydronaphthalene, acommercial solvent of the empirical formula ClOHlB, a saturated aromatichydrocarbon) This solution was miscible 1:2 with hexane withoutprecipitation.

(m) Another organo titanate, having aliphatic groups was used:

15.5 g. tetra isopropyl titanate were mixed with 19 g. winter sperm oiland 3 g. di-tertiary butyl peroxide were added. The resulting materialhad a slight tendency to fume at room temperature. On heating up to 1380., strong white fumes were formed and 5 g. material escaped. A slightreddish mass formed which was soluble in petroleum solvent. Noprecipitation occurred upon adding as much as 3 parts of solvent to 1part of the compound.

(n) The process of Example (m) above was repeated using the sametitanate with boiled linseed oil mixed with 5 g. tetra isoproplytitanate and 1 g. acetyl peroxide. The material was heated up to 145 C.and a red brown fluid was obtained which was soluble in mineral spiritand gave a clear flow on a glass plate and which dried at 100 C. overnight into a transparent dry film.

(o) In another modification, 17 parts of a non drying vegetable oil,olive oil, were mixed with 10 parts tetra isopropyl titanate and 2 partst-butyl perbenzoate. Heat was applied and vapors were formed at aroundand above 90 C. Heating was continued to 140 C., resulting in areddish-yellow oil with a tendency to a slight surface skin formation.The reaction product was found to be soluble (1:1) in benzol.

(p) 25 parts of sardine oil (LCP 40) were mixed with 21 parts of a 1:1mixture or two organotitanates; namely, tetra isopropyl titanate andbutyl titanate. 3.5 parts l-butyl hydroperoxide were added and heat wasapplied. Strong fuming occurred around 100 to 120 C. Heating wasdiscontinued around 150 C. and the liquid was thinned (1:1) withtoluene. A brownreddish solution was obtained. Adding 1:1 hexane did notcause precipitation of the solution.

(q) parts sorbitol-soybean oil fatty acid ester (a synthetic oilproduced by the Atlas Powder Co., G-876) were mixed with 5 parts tetraisopropyl titanate and 1.5 parts granular p-chlorobenzoyl peroxide wereadded. Upon heating to around 90 C., strong foaming began. Heating wascontinued up to 150 C. and a uniform light brownish oil was obtainedwhich was soluble in mineral spirits.

(r) Using another aromatic alkyl titanate, the phenyl titanate, which isat room temperature a solid mass. Using a smaller quantity; that is,parts phenyl titanate, softened at 100 C. in an oven, were heated with21 parts boiled linseed oil,

and 2 parts of an organic peroxide (Uniperox). At around 100 C., abrownish mass was formed. Heating was continued up to around 150 C. anda heavy viscous oil was obtained which was soluble in xylene.

(s) 10 parts phenyl titanate were slowly melted and mixed with 11 partssoybean oil and 1.8 parts tertiary butyl hydroperoxide were added. Onheating around 120 C., a dark, uniform compound was obtained which wassoluble in petroleum solvent.

(25) 11 parts of the synthetic oil used in Exampie (g) above were mixedby slow melting with 9 parts phenyl titanate at around to C.

2 parts di-tertiary butyl peroxide were added and heated. Gasdevelopment was strong around and above 100 C. Heating was continued upto 150 C. at which point 2 g. volatile matter had escaped. 3.5 parts ofthe resulting uniform, dark melt was dissolved (1:1) in benzol and aclear solution was obtained.

(it) 5 parts phenyl titanate were slowly melted with a mixture of 5parts of a semidrying vegetaable oil (saiiiower oil) and 1.5 parts of anondrying fish oil (sardine oil). A cloudy product was obtained uponadding 0.9 part of the diacyl peroxide of lauric acid (commercialAlperox C), which, upon heating, turned into a clear melt. Heating wasdiscontinued around C. The melt gave a clear drop on glass and wassoluble in mineral spirits.

(v) 13 parts menhaden fish oil were mixed with 11 parts butyl titanateand 2.5 parts of 60% methyl ethyl ketone peroxide in dimethyl phthalate(commercial Lupersol DDM). On heating to 80 C., the mixture became clearbefore all the oxygen had been released.

(w) 1. 11.5 parts butyl titanate (viscosity of 8 poises) were mixed with10 parts bodied linseed oil. 1.2 parts cumene hydroperoxide (74.9%) wereadded. On heating up to 120 C., a clear melt which was soluble intoluene was obtained.

2. 17.5 g. safflower oil, a semi-drying oil, were mixed with 12.5 g.butyl titanate and 1.8g. cumene hydroperoxide. At C., a clear andsoluble product was obtained. The example was repeated at 65 C. 14 partssafflower oil were mixed with 13 parts butyl titanate and 2 partscurnene hydroperoxide. Heating was limited to the point when the firstgas bubbles began (65 C.) and the vessel was held at that temperaturefor 5 minutes.

3. 12 parts soybean oil and 10 parts butyl titanate were mixed with 0.5part cumene hydroperoxide and reacted at the initial gas bubbletemperature (65). A clear product was obtained.

1.12 parts candelilla wax were melted, and at a temperature of 75 C., 10parts butyl titanate were added, along with 1.7 parts of 60% methylethyl ketone peroxide (in dimethyl phthalate). Heating was discontinuedand the temperature rose from 75 C. to 100 C. As soon as cooling began,the mixture was heated up to 140 C. The mass was then dissolved in xylol(about 1:12) and a clear solution resulted. On cooling, a slight waxycloud was observed.

2. 15 parts carnauba wax (clear, light type) were melted, 10 parts ofbutyl titanate were added, and 1 part t-butyl perbenzoate were used. Onheating to C., a uniform melt was obtained which was uniformly solublein warm toluene.

3. 14.5 parts of a synthetic wax-like substance, ethylene glycol (mono)ricinoleate (commercial type 8-152, Glyco Products Co.) were mixed withenco es:

11.5 parts butyl titanateiandlfi parts cumene hydroperoxide(techn-.175%) :heated up to around 120 C. A uniformrproduct.was'obtained and dissolved (1:1) in xylol. The resulting warm solutionwas clear and on cooling, a soft waxcondition was obtained:

4. parts: polyethylene glycol di-oleate (S. 1011, Glyco-Products) weremixed with 9 parts butyl titanate and 1 part di-tertiary butyl peroxidewere-added. On warming, two layers were observed, but a uniform waxsubstance was obtained at around 90 C. to 100 C. under the effect of theperoxide.

Example 2.C'ompoanding an alkyl titanate and a polyhydrz'c fatty acidester into a'gel It is shown in the present example that gelling can beaccomplished and a product can be produced which will be suitable forresolubilization as an oil gel if treated in accordance with the methoddisclosed and claimed in U. S. Patent 2,476,879.

(a) 4 1 parts of a reaction product obtained in accordance with Example1(0) were mixed with 13 parts of the same synthetic oil, heated with 4parts of the same catalyst under occasional stirring. Between 170 and180 C. gelling occurred. This gel was applied hot to a glass plate andbaked on at 100 C. during several hours into a coherent film.

Another part was swollen into hot toluene (1:1) into a liquidappearance. The compound gelled on cooling. Baked onto a glass plate, itformed a coherent film.

(b) 29 parts butyl titanate were mixed with 5.2 parts t-butylperbenzoateand heated. At around 100 C. some reaction and gas formationwas observed. Heating was continued to around 189 C. to 190 C., at whichpoint a resinification occurred. On cooling, a brittle resin wasobtained. No gelation was observed.

(0) parts tetra cyclohexyl titanate were mixed with 15 parts tungoil and3 parts t-butyl perbenzoate and quickly heated to about 160 C'., wherebydarkening occurred and the temperature increased under gas developmentup to and above 200 C. Three grams of substance had evaporated duringthe procedure. The compound was allowed to cool to about 70 C. and 2more parts of the catalyst were added. Heating was applied to about 180C. A strong reaction was observed, and the temperature raised rapidly toabove 220 C. Heating was continued under stirring up to 260 0., wherebya brown, somewhat smeary gel was obtained whichwas atleast partiallyinsoluble in hot xylene. 6.5 grams of volatiles evaporated during thereaction.

(d) 22.8 parts of thesynthetic oil used in Example 1(g) were mixed with9.2 parts butyl titanate and 2 parts tetra isopropyl titanate and heatedwith 3 parts t-butyl hydroperoxide. A strong reaction occurred aroundand above 110 C. Gelling occurred at 175 C.

(e) 13 parts ofthelinseed oil-phenyl titanate compound, as produced inExample 1(r), were heated with 2 parts of the same peroxide and at 1300., gas formation was observed. Gelling occurred at around 180C.

(f) 1. 18.2 parts-of the candelilla wax-organetitanate compound ofExample 1(y-1) were treated with 1.8 parts methyl ethyl ketone peroxide(60%). Around 120 0., strong foaming occurred and a solid gel. wasobtained.

2.21.5 parts ethylene glycol mono-ricinoleate .organo-titanate. compoundproduced in ExampleHy-E) were treated by heating with 2 parts ofcumenehydroperoxide (75% tech). Around C., solidification occurred.

(9!) 23 parts industrial accelerated -linseed oil (Castung 504Z-3, BakerCo.) were mixed with 11 parts butyl titanate and 2- parts ditertiarybutyl peroxide were added. On heating, the mass became uniform around110 C. On quickheating up to around 215 C., a strong gel was formed,which, on cooling, had atendency toward brittleness.

Example 3.--Resolubilizing the alkyl titcmatepolyhydric alcohol fattyacid ester gel (as) The gel produced in' Example 2(a) was resolubilizedby heating witlra metal soapcatalyst as follows:

50 parts of the gel were swollen in 50 parts hot toluene, and thisproduct was mixed with 14 parts of a standard lead-naphthenate liquid(24% Pb). On heating, the volatile solvent escaped and theremainingmasswas-further heated to about 0., at which point a tough,high viscous state was observed. 5 more parts of the same metal soapcatalyst were added. On heating, a thinmelt was obtained: around C. Thiswas soluble 1:1 in toluene, and on applying this clear solution to aglass plate, a clear film was obtained by baking at 100 C. for 2 hours.

(b) The gel produced in Example 2(0) was resolubilized as follows:

25 parts of the gel were mixed-with 7 parts lead octoate liquid (24%Pb). On holding the mixture at around and above 170 C., the 2.8partssolvent.containedin the liquid commercial metal soap evaporated andthe gel melted into a uniform liquid state. This was dissolved 1:1 inxylene and filtered. Less than1.5 g. swollen surface-skin were found;The other 235g. of the gel had clearly been dissolved-and the solutionremained clear on standing for 24 hours. Appliedasa coating on steelanddried at 100 C., a coherent film with glossy appearance was obtained;

((2) The gel produced in Example 2(cl) was resolubilized as follows:

10 partsof the gelwere resolubilized by heating with. 4 partscopperoleate in the presence of 1 part synthetic isomerized castor oil(commercial Dienol OC .101-, Oil-Chemie Inc, Hansen, Switzerland).Fusing occurred around 155 and 210 C. Heating was continued understirring up to 225 C. and the mixture was obtained as a uniform fusedcompound which was soluble and stable in a 1:1 xylene solution (d) 18partsof the gel produced in Example 2(e) were reliquefied-by fusing with6 parts of a metal soap solution (commercial cobalt naphthenate, 6% 00)..Uniform melting occurred around 130 C. Heating was continued up to C.-About 2.4 g. of volatile matter evaporated from the solution, and theliquid melt was dissolved in 18 g. xylene. A uniform, fullyresolubilized product was obtained.

(e) An excess amount of organotitanate is used such surplus beingdetected-after resolubilization of the gel in-the form of granular,insoluble particles which are identical to those obtainable by heatingan alkyl titana-te with an organoperoxide. In the following experiments,the percent of organotitanate was further increasedto 1.5 parts (2 partsfor 2 parts of oil):

1. 24- parts-bodied linseed oil were mixed with 14 parts butyl titanateand 3 parts 1-hydroxy cyclohexyl hydro peroxide-1 were. used. A stronestates 9 reaction occurred around 130 C. and strong gelling occurred at175 C., resulting ina resinous jelly appearance. Upon adding 14 parts ofa cobalt tall oil metal soap liquid commercial Co Nuolate with 6% Co)and heating again, melting occurred between 150 C. and 210 C. understirring. On thinning, about 2 g. of a granular, undissolved matter wasfound which was identified as a derivate of the excess organotitanate.

2. The test was repeated using the same amount di-tertiary butylperoxide as catalyst and using 6 g. manganese linoleate as the metalsoap. Melting occurred around and above 160 C., and about 1.8 g.granular matter remained on filtering.

(f) 36 g. of the gelled accelerated linseed oilbutyl titanate reactionproduct of Example 2(g) was heated with 18 parts of a lithium-resinsoap, prepared by melting 30 parts wood rosin and gradually adding partslithium carbonate, and continuing the heating until foaming receded,followed by heating up to 225 C. The gel-rosin soap mixture was heatedunder stirring until a clear melt had been obtained around 235 C. Theproduct was dissolved in 50 parts xylol under heating. On filteringthrough cotton cloth, less than 0.5 g. of a slight skin remained on thecloth. A clear solution was obtained.

1. The candelilla Wax-organotitanate gel of Example 2(f-l) wasreliquified by heating 18.2 parts with 18 parts liquid zinc naphthenate(8% Zn) up to 225 C.-230 C., until melting had occurred. The melt wasdissolved in 20 parts xylol. Less than 0.5 part undissolved matterremained on the filter cloth. 7 In warm condition, a clear solution wasobtained which, on cooling, exhibited a waxy appearance.

2. 21.5 parts synthetic wax-organotitanate gelled solids of Example2(f-2) were reliquified by heating with 13 parts lead oleate up toaround 240 C., at which point melting occurred. The melt was dissolvedin 22 parts xylol. The initially clear solution turned to a slightlywaxy appearance on standing.

(9) 15 parts of an organotitanate oil gel were prepared by rapidlyheating a mixture of 15 parts bodied linseed oil and 10 parts butyltitanate with 2.5 parts organoperoxide (methyl ethyl .ketone peroxide,60% in dimethyl phthalate) up .110 around 140 C., at which point gellingoccurred. parts of the gel were resolubilized 'by heating with 10 partslead soap (prepared by heating 15 parts candelilla wax with 5 parts leadacetate up to 145 C.) under stirring up to about 195 C. The resultingmelt was dissolved in 2.5 parts hot toluene. On cooling, the resultingsolution had a waxy appearance. On warming up to around 50 C. to 70 C.,the solution became clear and on cooling, the material again returned toa soft, soluble and fusible wax.

1. 12.5 parts beeswax were melted and mixed with 10 parts butyltitanate. 2.5 parts tertiarybutyl perbenzoate were added. I On heating,strong foaming occurred above 110 C. On heating up to 155 C., a uniformmelt was obtained. In a second step, 2 parts of perbenzoate were addedafter cooling the melt to about 100 C. On heating up to about 185 C.,the uniform melt remained stable and no gelling occurred. After coolingto about 90 C., one part perbenzoate was added, and on heating up to 190C., a coherent gel was obtained which was similar to oil gels and formeda long and coherent thread of gel substance when dropped in drop formfrom a glass rod.

20 parts of this gel were resolubilized by heating with 10 parts of ametal soap product derived from wax. The latter was prepared by heating18.5 parts beeswax with 5 parts manganese acetate. After foaming (aroundC.), heating was slowly continued to 215 C. On heating thebeeswaxy-organotitanate gel with the beeswax metal soap up to 225 C., aclear melt was obtained. Drops thereof did not show a gel-like behavior,but fell individually without a streak formation. The reaction productwas fully solu- Example 4.Compounding an alkyl titanate with a siliconeresin material Examples of the compounding of silicone resins with alkyltitanates in the presence of free oxygen-releasing, organoperoxides areas follows:

(a) 21 parts butyl titanate were added to 30.5 parts of a 60% commercialmethyl phenyl silicone resin (Dow Corning product DC 801) identifiableas a phenyl methyl polysiloxane, which is highly substituted andtherefore, relatively flexible and thermoplastic. 4.5 g. p-chlorobenzoyl peroxide were added. On heating the mixture slowly understirring, foam formation was observed around 100 C. At C. a clearbrownish solution was obtained. Heating was discontinued around C. Theloss in weight was 15 g. which corresponded approximately to the solventcontent of the silicone material and the volatile substance of theperoxide.

On standing, the substance showed a slight tendency to form a thinsurface skin. It was diluted (1:1) in toluene, applied to a glass plate,baked for 20 hours at 100 C., and a clear film was obtained having SwardHardness 58.

The solution was further modified by mixing 20 parts of the 50% toluenesolution with 5 parts I tung oil, and a clear and stable solution wasob-. tained. This was applied to a glass plate and baked at 100 C. for20 hours. The film showed at some areas the usual slight wrinkle effectof tung oil varnishes. On other areas, a clear film was obtained havingSward Hardness .34.

This solution also was mixed with a pigmented phenolic resin varnish inthe proportion of 3 parts to 1 part of the pigmented varnish. Thisvarnish was a pure phenolic tung oil varnish, produced from 25 partsphenolic resin (Bakelite BR 254) with 24.5 parts tung oil at around 450F., thinned with 49.5 parts xylene and modified with 0.05% lead and0.006% cobalt-naphthenate driers calculated on the oil. In pigmentation,400 parts of this phenolic varnish were thinned with 20 parts xylene and75 C. P. toluidine toner.

This colored modification of the silicone resinalkyl titanate compoundwith a phenolic resin tung oil varnish and pigmentation was applied to asteel panel, dried at 50 C. overnight and had a Sward Hardness 30.Applied on wood treated with a shellac solution as filler, a colored,semiglossy film was obtained.

The product was compared with the untreated silicone resin solution asfollows:

(1) Both solutions were applied to steel panels and dried at 100 C. for18 hours. The initial silicone resin remained uncured and very tacky.

The new product had formed a dry and'fiilly tack-free coating.

(2) Both solutions were mixed with tung oil (2:1). The initial siliconesolution wasnot compatible with the oil, and in a very few minutesassures 11- a brownish precipitation was formed. The new compoundforme'd'a stable clear solution.

(b) 17 parts butyl titanate were mixed with 30 parts of a 60% commercialmethyl phenyl silicone resin, (DC 804) and parts(ii-tertiarybutylperoxide were added. On mixing, a transparent gellyprecipitate occurred. This silicone is identifiable as a phenyl methylpolysiloxane, which is of lower substitution, and relatively rigid andthermosetting. On heating, foaming began around 65 C., and was strong ataround 125 'C. Auniform solution was obtained. On heating up to around175 C., a light colored melt was obtained, being in color lighter thanthe commercial silicone resin DC 801 used in Example 4(a). 17 partsvolatile solvent and catalyst material had escaped. The reaction productwas thinned with toluene (1:1) and a clear, light brownish liquid wasobtained.

'This' solution was miscible with tung oil (2 parts new solution and 1part tung oil). The commercial silicone resin solution (DC 804), thinnedto the same 50% concentration, formed witntung oil a colored jellyprecipitation, on standingfor a few hours.

The new products produced in Examples ((1) and (bl were compared ascoating compounds with the silicone resins DC 801 and DC 804 in 50%toluene solutions. All four were applied to steel panels and baked at100 C. After 18 hours, both silicone resins were very tacky. Bothtitana'te compounds were dry and fully tack-free.

Aiter42 hoursthe silicone coating (DC 801) had at room temperature aSward Hardness l6. Itsallryl titanate compound made a Sward Hardness44;. The silicone coating (DC 804) had at room temperature a SwardHardness 46, and its titanate compound had a Sward Hardness l4.When'testedagain at 100 C. the DC 804 silicone had softened to 36, andthe allzyl titanate compound had softened to 42, thus indicating theimproved curing characteristics of the new compoundsf (c) 20.2 parts ofa solution of phenyl methyl polysiloxane (DC 803, which is relativelyreactive and quick drying), 50% in Ennjay 3 solvent and toluene, weremixed'with '7 parts butyl titanate and with 2.7 parts'tertiary-butylhydroperoxide and stirred. A jelly colorless mass was obtained. Onheating to around 90 0., the temperatiue went up rapidly to around 106C., and a gelled, popcorn-like solid product was formed.

1. Onmixing 20 parts commercialDC 803 solution (50%) with 8.1 partsbutyl titanate and stirring, a jelly mass was obtained. On adding 0.3part'tertiary-butyl-hydroperoxide with 0.4 part toluene as diluent andheating slowly, the substance became progressively more uniform. Around170 C., a clear, slightly reddish colored melt was obtained, whichformed (1 part melt and 1.2 parts benzol) a clear and stable solution in1.2 parts benzol. In contrast to the initial DC 803 solution, the newsolution was clearly miscible with butyl titanate.

(d) 30 parts of ethyl silicone resin (commercial 0-25, 50% solution)which had gelledin storage to a tough, coherent gel, not capable ofbeing diluted clearly, were mixed with parts butyl titanate. 09 partl-hydroxy cyclohexyl hydroperoxide-l, a macrogranular commercialproduct, was added. On heating the mixture slowly, a very tough jellymass was formed around 60 C. and the granular peroxide melted into themass under slight gas development. At 80 C. the gas developmentincreased, the gel softened, and the temperature-roserapidly to 115 C;Heating wa'scontinued to about. 140 C. The product was substantiallycompletely dissolved(1:2) in benzol, with only a very few popcorn-likeparticles remaining on the filter. The solution was applied to analuminum panel and dried overnight at 150 C. into a tough, dry coating.

1-A. 21 parts butyl titanate were mixed with 10 partscyclohexenyl-polysiloxane (commercial X-32), solution, and with 10partsethyl silicone resin"(C-25) in solution, and an incompatiblejelly-like' mass was obtained. 1.2 parts di-teritary-butyl-peroxide wereadded. On heating up to 140 C., foaming was'obse'rved. A clear liquidwas formed which was (32p'arts) dissolved in toluene (32:22) and acleartransparent solution was obtained.

1-13. 20 parts butyl titanate were mixedwith 13.5 parts ethyl siliconeresin (50% solution of commercial (3-25) and with 8.5 parts methylphenyl silicone resin solution of commercial DC-l). O-n mixing, ajelly-like precipitation was observed. 2 parts of xylene were added with1.7 parts tertiary-butyl-perbenzoate. The mixture was heated, and slightfoaming occurred around C., with the jelly mass becoming more and moreuniform. Under stirring a clear fused state was reached around to C. Apart of the product was dissolved in toluene. (1:1) and ayellowish-colored clear solution was obtained which remained stable for30 hours.

1-C. To 28 parts of 'the fused .product of Example 4(d)1-B, were added 5parts lard oil,along with 0.4 part tertiaiy butylperbenzoate. Aftermixing, a drop taken out with a glass rod fell with jelly-likeappearance. Heat was applied, and between 90 C. and 100 (3., a clearfused state was observed. The product was heated to about C. underfoaming. About 2 parts volatile matter evaporated. The product wasdissolved in 24 parts toluene, and a clear reddish solution wasobtainedwhich remained stable and showed no precipitation after 30 hoursstanding at room temperature.

l-D. 15 parts butyl titanate were mixedwith 13 parts ethyl siliconeresin (50% solution). and one part cumene hydroperoxide (74.9%). 2 partsxylene were added for better dispersion of the peroxide, On mixing, ajelly-like incompatible mixture was obtained. On heating'slow ly up to120 CI, the mass became uniform, liquid and transparent. It dissolved in20 parts toluene without residue.

2. 20 parts of a shelf-aged, strongly gelled, 60% commercial siliconeresin (DC 801) were mechanically mixed with 6 parts butyl titanate, and0.6 part fine powdered 95% benzoyl peroxide (with 5%"stearic acid) wereadded. Thejmixture began to melt at around 140 C., and heatingwascontinued to C. Afew particles remained unfused, and the amount ofalkyl titanate was somewhat increased by adding 0.6 part butyl titanate,'and the heating was repeated. The reaction product was dissolved in 11parts solvent, 'or tetra-hydro-naphth'alene solvent, and further dilutedwith i par s xylene. The product was completely soluble with theexception of 0.5 part undissolved popcorn-like substance. On an aluminumslate at'100 Covernight, the clear solution produced a tough coatingwhich was tack-free even at the oven temperature. i w

a 3. 20.5 partsbutyl titanatewere mixed (similar to A) with 11 parts0-25 ethyl silicone resin (50% solution). 1.5 parts of commercial methylethyl ketone peroxide (60%), commercial Lupe'rsol DDM, were added. Onstirring, a jelly-like, irregular mass was obtained. Slow heating underoccasional stirring around 125 C. to 130 C. developed a uniform melt.Heating was continued until a clear liquid state had been reached ataround 170 C. A sample was dissolved in xylene and formed a clearsolution. On cooling, the melt itself had a tendency to form a thinsurface skin.

4. To 20 parts of the product from 3 supra, 5 parts of a polyhydricalcohol fatty acid ester oil, teaseed oil, were added. At around 70 C.,one part of the same peroxide was added. The temperature rose quickly toabout 100 C. under foaming. After the reaction slowed down somewhat,heat was applied to about 130 C., and the product was dissolved in 30parts toluene. A clear solution was obtained. On filtering, less than0.5 part thin skin was recovered.

5. 32 parts butyl titanate were mixed with 13 parts vegetable oil(soybean oil) and with 17.5 parts ((3-25) ethyl silicone resin solution(50%). 3.5 parts tertiary-butyl-hydroperoxide were added. On mixing, ajelly mass was observed. Heat was applied. Around 110 C. some gel matterremained. Under some foam development and stirring the heating wascontinued to around 135 C. The mass was primarily uniform, and at about160 0., a completely uniform melt was obtained which dissolved (53:40)in toluene, to give a clear, completely dissolved product. The solutionwas observed after several hours of standing at room temperature, andremained clear.

(e) 21 parts commercial silicone resin, DC 801 (60% solution), weremixed with parts tetra-cyclohexyl titanate. The mixture was notcompatible. 3 parts tertiary-butyl perbenzoate were added and the masswas heated. Foaming occurred near and above 100 C. and the productbecame a uniform liquid. The foaming increased on continued heating, notonly due to the peroxide, but also due to the escape of the volatilesolvent. 5 g. substance evaporated. Heating was ended around 165 C. andthe product was dissolved (1:1) in xylene. A clear stable solution wasobtained. As a coating material, it dried in 90 minutes at 100 0. into atack-free coating on a steel panel.

(1) 21 parts of a commercial methyl phenyl silicone resin (DO 996), 50%solids, were mixed with 9.5 parts tetra-cyclohexanol titanate and amixture of peroxides comprising 1 part tertiarybutyl perbenzoate and 05part acetyl peroxide (in dimethyl phthalate). Strong foaming occurredaround 100 C. to 120 C. Heating was continued to around 180 C. 20 partsof a reddish compound were obtained, which compound was fully soluble(1:1) in toluene.

This solution was further diluted (1:2) with xylol, and then again(1:05) with butyl titanate, and then (1:1) with dehydrated castor oil.It was not possible to mix it (1:1) with a silicone solution, DC 996(50% solids), because of gel precipitation such that additionaltreatment with organoperoxide would have been required.

(g) A commercial thermoplastic methyl phenyl silicone resin (9989-1,General Electric) was mixed with 5 parts butyl titanate and 2 parts of avolatile VMP naphtha was added for ease of mixing. The mix was notuniform. 2 parts of commercial organic cyclic hydrocarbon hydroperoxide(Uniperox 60) were added. Strong '14 foaming occurred, especially above110 C. and around 130 C. to 150 C. Heating was discontinued around 170C. 7 parts volatile matter had escaped. The uniform compound was dis-.solved in 17 parts Decalin (decahydronaphthalene). This uniformsolution was not compatible without additional treatment when mixed withsoybean oil (1:2). It was clearly soluble (1:1) in xylene, and 1 part ofthe initial silicone resin (9989-1) was added without precipitation. Theuniform solution was clearly miscible with amyl triethoxy silane(1:0.8), as well as (1:1) with butyl titanate and with a mixturethereof.

(h) A silicone resin and tetra-isopropyl titanate were compoundeddirectly by mixing 40 g. silicone resin (9989-1, General Electric) with15 parts tetra-isopropyl titanate, whereby a jellylike condition wasobtained. 2.8 g. tertiary-butyl hydroperoxide were added, and themixture was heated slowly. At above C., slight boiling was seen whichbecame stronger at and above C. The heating was continued to around 120C. 10 g. volatile matter had escaped from the peroxide, and the solventwhich was part of the commercial resin solution.

in about 20 minutes. After 16 hours at C.,. it was very hard and was notscratched by the: fingernail.

1. The product of Example 4(h) was plasticized. by mixing 1:1) withtricresyl-phosphate. Tobutyl titanate was added (1:2) this product, anda clear solution was obtained on mixing. This. was modified by furtherdiluting with xylene (1:1). The solution was applied on a glass plateand baked at 10 C. for four hours. A dry film was obtained which had aslight cloudiness along the edges.

(2') 20 parts phenyl titanate, a hard mass at room temperature, wereslowly melted in 30 parts. silicone resin solution (9989-1, GeneralElectric) A yellowish-red suspension was obtained. 3 parts: di-tertiarybutyl peroxide were added and the: mixture was slowly heated until warm(around. 150 0.), and a clear fused liquid resulted. A sample was clearand soluble (1:1) in toluene, and gave a clear, transparent flowout. Oncooling, a yellowish cloud was observed which apparently was caused by aslight surplus of phenyl. titanate.

1. The product of Example 4(2') above was: combined with 12 g. of asynthetic bodied oili (commercial Neo Fat 290 of the Armour Com-- pany),less 3 g. used for solubility test, and 23 parts of the same peroxide.Heating to around 150 C. caused strong foaming, whereby a product wasobtained which was not only soluble in hot toluene, but which remained aclear, transparent reddish-brown solution on cooling to roomternperature and standing for several hours. The slight surplus ofphenyl titanate appeared to have been used in this step of the reaction.

2. The preceding test was repeated, using somewhat more titanate. 20parts phenyl titanate were mixed and melted in 24 parts of the samecommercial silicone resin (General Electric 9989-1) and 2.8 partsdi-tertiary butyl peroxide was added. Gas development began around C.,and became stronger around C. Heating was continued to around 0., whenonly a relatively slight yellow cloud remained in the fused material. 12parts volatile matter had escaped. One part of the material wasdissolved 25 g. xylene was. added and a straw colored solution wasobtained, which gave on glass 2. clear, transparent fiowout... It wasbaked at 100 C. and was dry to the touch;

.1 in. xylene (1 1): and a a stronger cloud-uwas iound than. in Exampleas) above. '1 However, thematerialbaked. at 1005C. in'two hoursinto acoherentzfihn.

3. 18: parts: of i'the preceding reaction product (without solvent)"-were .further heated with 5 parts of the synthetic oilzas.used:.in;;Examp1e 4(i-1) .zabove. and. 1;. part (ii-tertiary hutylperoxide was added; -zOn heating up.to 180'C.,.1.4 g. volatile matter:escaped 1 and. the substance. in tolueneilzl) gave a clear solutionwhich baked in two hours on. a'giass plate atlOO". G. into. a clear,hardfilm.

4. The siliconeralkyltitanate oil compound in toluene obtained from;Example 4(i-i1)==was mixed with that .fromiExamplei Hi-'3) and;they werefound to -bezzmiscible. The mixture was :diluted with xylene (12-1)andjagain a. clear solution was obtained. '1 This solution was mixedwith soybean oil (2:1) and a;clear solutionwas obtained on shaking.

For comparisonjhe initialcoinmercial silicone resin solution(General.Electriczil98 l) was diluted with xylenelz 1) and soybean oil(2: 1) was added. On shaking, a .flocky precipitatewas formed;thereby'evidencing that the silicone resin had reacted zandzr had beenmodified. :in-the processes of Examples .4:(11-11) and I -(i-3) above.

(It) 30.5: parts. methyl phenyl isilioone resin (General Electrie 1182);6.0% solids in xylene, were mixed with 12 parts butyl titana-te. Onmixing, a slight :gel was-x obtained. 2.1. parts methyl ethyl ketoneperoxide (60% "in .diinethyl phthalate) were; added and' the mixture washeated. Around-.80? C.,:strong foaming-occurred. On heating to about1-10"- C., isome darkening occurred and 2.5.parts1volatileamatterescaped. The compound was. thinned'with lflparts toluene and:a-clear reddish solution was .obtained. -It was modified by adding(1:1.5)mcycloehexenylpolysiloxane (X 32),4..45%:-in:. itoluene,andwremained. clear.

. (Z) .g. .butylititanate were. mixed withildg.cyclo-hexenyl.polysiloxane; (Linde Silicone X+32) 45% solutionintoluene. .1.8.g.:cumene--hydr-o. peroxide were added and the mixture wasslowly .heatedrunder mixing. .T-herproductrturned uniform: at." around.efitcuand became light incolor, indicating that areactionylas under:-way. At 130 C. alight brown product :was: obtained whichwasdissolvedinrlO g-. xylen e:and.=r.emained stable overnight.

(m)- 9.5 .g.1butyl titanate were mixed with .10 g. vinyl tpolysilo'xane.(Lincles .Silicone X;31r-in 50% toluene-solution) and 1.g..cumenehydroperoxide wereadded. On stirring, ageliwas obtained. On carefullyheating. under; stirring, the gel began to disappear around-.C. At C.,the heating was discontinued, but the mixture continued to .rise intemperature. up to 60 C. Aclearproduct was .obtainedwhich was fully.soluble and stable in 10 g. xylene.

12 g. butyl 'titanate were: mixed .with .11.4* g. vinyl polysiloxane.andrlfi g.;cumene 1hydroperoxide. The mass was .cleanand..uniform.:onheatingto around '80?- Clybutat around 100: (2., it turnedinstantaneously into a solid; insoluble and: incoherentv state,'-.as:describedin .myaSerial No. 33,676.: thereby illustrating ythe secondaryreaction caused byrrthevinyl group.

Example. 5.-.-Compounding .the' reaction prodacts of Example I-wz'th-ctsilicone resin 'It has been-shown -in- Example -1that -alkyl titana-tesand oils; etc.,- dorm reaction products 16 which vcarrbe .modified by;mixing them with other oils, alkyd resins, .etc. It has beenshown inExample ithat .alkyl titanates and silicone resins form reactionproductswhich. can bemodiiied by mixing with oils, ,varnishesidriers, etc.

The present example, is concerned with the compounding of. the reactionproducts :of, Example 1 with silicone resins and silicone resincompounds-in. the presence of free oxygen releasing organoperoxides.

(a) 10 parts of the reaction product on Example 1(i) were dissolvedin 20.parts :of a commercial silicone resin varnish .(DC. 996, solids). and10 parts xylene were added. A clear solution was obtained without theaddition. of either an organoperoxide -or:.heat,.whiclrproduced a clearfilm on azglass plate when: baked at around 100C.

- On the other hand, when theinitial Isolene oillwas added to the samecommercialisilicone resin in xylene solvent in the same proportions asin Example 1(12), a jellyelike product .was obtained which would notform a clear solution.

(b) VJhen 28 parts ofthe reaction products oiiExample 1(k) were mixedwith 14 parts :of

thesame commercial silicone resin varnishes used in Example 5(a)..aoove,a jelly-like. mass was formed. 3 partsdi tertiary butylperoxide 'wereadded as an organoperoxide .andsthetmixture was heated. Strong foamingwas observed around 140 to 160C. {Heating was. continued up toabout 215C. About 11 parts volatile substancehad escaped, including'the '7 partssolvent. present .in the'silicone resin varnish and 3 parts of theorganoperoxide. The product was clearly soluble in 32 parts toluene.

(0)23 parts of thereaction productLof Example -1(g)' were mixed. with 12partssilicone resin varnish (DC 804, 60%v solids) .and d'parts acetylperoxide in dimethyl phthalatewere used. Strong foaming occurredbetweentlOO" and 130 C. Heating was continued-up to about 220 C. atwhich point vapor developed. Bparts substance hadescapedasvolatile-:rnatter; The reaction product was a resinous,-jelly-like massof slight reddishappearance. Under' boiling in 46.;parts toluene, aclear solution was obtained. It was appliedon Inconel panels, baked atC., and clear; .dry coating films. were obtained.

(-dX-Theproduct of Example 1(m).:was compounded with a siliconeresin,'26.5 g. beingrnixed with .20. parts; commercial silicone resin.solu tion (DC..803, 50%). The resins-.were -not miscible and thesilicone resin formed large agglomerations of 'jeliy like substance.Ascatalyst, 3 parts commercial cycle-hydrocarbon hydroperoxide(UniperoxrSO) were added. :Boiling. was observedaround 0., and mostxofthe-gel went into solution. At 0., a-fewundissolved particles remained.Heating was discontinued, and the material was. permitted to cooLtoaround 80 'C. 5 10 parts volatile substance .had escaped.2..partst;Uniperox were-added, and heating was continuedup to around C:5 g. volatile matten-had escaped. Aweddish, clear melt was obtainedwhieh'dissolved in 30 parts xylene. A solution. was obtained whichformed-on a glass plate ascle'ar film whendried at 100 C. for two hours.*The fi1m,-after '16 hours-at 100 C., remained-somewhat softwhenscratched with the fingernaiL -but was otherwise a dry 'film, eventhough a non-drying oil-hadbeenused.

Xe) The product obtaine'd -in-Example 1(0) was compounded by mixing =24par'tswith 21 parts silicone resin '('DC 801, 50% solution) anda'dd- 1?ing 2 parts tertiary-butyl perbenzoate. On mixing, a jelly-like mass wasformed. At 140 C., no fusing had occurred. The amount of titanate wasincreased by cooling the mass to about 100 C. and adding 5 partstertra-isopropyl titanate. Heating was continued to 160 C. 11 partsvolatile matter had escaped. Upon adding 40 parts xylene, a reddish,transparent solution was obtained which was applied to a steel panel anddried in an oven at 100 G. into a dry coherent film.

(f) 30 parts of the product of Example 1(p) were mixed with 14 partssilicone resin solution (General Electric 9981-1). 2 partstertiary-butyl hydroperoxide were added. A jelly-like mixture wasobtained. Slow heating to 125 C. developed a uniform melt. Afterthinning with 20 parts benzol, it was applied to a steel panel and driedat 100 C. into a hard film. A clear solution was thus obtained withoutadditional titanate being added.

1. The rate of reaction was increased by doubling the amount oforganoperoxide, as follows: 30 parts of the reaction product of Example1(2)) were mixed with 14 parts silicone resin solution (General Electric9981-1). tertiary-butyl hydroperoxide were added. A jelly-like mixturewas obtained. The rate of reaction was such that at 110 C., rapidsolidification into incoherent, limited swelling particles occurredwhich were insoluble in coal tar solvents.

2. The preceding result was prevented by increasing the amount oftitanate as follows: 30 parts of the reaction product of Example 1(p)were mixed with 14 parts silicone resin solution (General Electric9981-1) and parts of the same organotitanate were added in a 1:1 mixtureof tetraisopropyl titanate and butyl titanate mixture. 4 partstertiary-butyl hydroperoxide were added. A jelly-like mixture wasobtained. The reaction was very strong around 70 C. to 80 C., and quickfusing was observed. On further heating, solvent evaporation caused somefoaming around 125 C. Heating was discontinued and 48 parts fusedmaterial was obtained and dissolved in 45 parts benzol. Completedissolving occurred, and the material dried on a steel panel at 100 C.into a dry film. The solution itself did not increase in viscosity onstanding for several hours.

(9) 21 parts of the reaction product of Example 1(r) were mixed with 9parts silicone resin (DC 801, 60%), and 1 part Uniperox was added. Aheavy jelly mass was obtained. On heating, gas development began around100 C., and the material began to fuse. 2 parts butyl titanate wereadded, and the heating was continued until the whole material had beenfused. on cooling, the product formed a rubbery mass which difiered froma gel in that it was capable of being dissolved on heating with 20 partsof solvent (decahydronaphthalene) This solution was further diluted withtwice the volume mineral spirits and a clear, reddish solution wasobtained. 7

(h) 16.5 parts of the reaction product of EX- ample 1(25) were mixed ataround 70 C. with 5 parts silicone resin (General Electric 9989-1) and0.5 part benzoyl peroxide (95% with stearic acid) were added. Slightgelling occurred, and on heating up to 160 C., 1.8 parts volatile matterescaped. The melt was thinned with parts toluene under heating to theboiling point, and a clear solution was obtained, which gave on i parts18 glass a clear fiowout and dried at C. in the oven in a film. 0nfiltering, no residue remained.

1. 2 parts of the preceding product were thinned with l'benzol and 1part soybean oil was added. The mixture wasshaken. No precipitationoccurred on standing overnight.

(1') 10 parts of mixed oil-phenyl titanate compound of Example 1(a) weremixed with 5.2 parts silicone resin (DC 996, 50% solids). Aheterogeneous mass was obtained with a jelly-like material floating onthe surface of the melt. 0.95 part of lauroyl peroxide were added, andthe mass was heated. Around 200 C., it fused uniformly. Heating wasdiscontinued around 230 C. and a clear melt was formed. 3.55 partsvolatile matter had escaped. The remainder was dissolved in 8 partsxylene, and a clear, reddish brown solution was formed which gave onglass a clear, cloudless fiowout.

(k) 12 parts General Electric silicone resin solution, 81182 (about 60%solids in Xylene), were added to the reaction mixture of Example 1(1))before all the peroxide had been used up, and the heating was continued.At first, the mixture was cloudy. Strong foaming occurred around 0.Heating was continued up to about 140 C. 4.5 parts volatile matter hadescaped. 15 parts xylene were added as solvent, and a clear, stablesolution was obtained.

(Z) 20 parts of the reaction product produced in Example 1(w-1) weremixed with 11 parts cyclo-hexenyl polysiloxane in 45% solution, and

05 part hydroperoxide were added. At 130 C. strong foaming occurred. Theresulting product was clearly soluble (1:0.7) in xylene and remained astable solution when observed over a period of three days.

(171.) The process of Example 1(w-1) were repeated with a silicone whichcontains an addi tional reactive vinyl group, Lindes Silicone X-31 (50%toluene), a vinyl-polysiloxane. The reactions of the present inventionoccurred, but care was required to obtain the reaction product in asoluble form. When greater amounts of peroxide were used, or a reactiontemperature above about C. to 155 C. was used, the reaction productsturned directly into incoherent and limited swelling popcorn-likemasses, as described in my pending application No. 33,676.

1. 30 parts of the initial reaction product of Example 1(w-2) were mixedwith 10 parts silicone solution X-31. A mixed gel was formed. 2 g.cumene hydroperoxide were added and heated under foaming up to 155 C.,whereby 5 g. volatile matter escaped. The product popped; that is,formed incoherent popcorn-like solids, and on adding 25 g. xylene, theincoherent solids were filtered oif and further purified by solventtreatment.

2. 27 parts of the second reaction product of Example 1(w-2) were mixedwith 11.5 g. vinylpolysiloxane solution. Heating was continued slowlyand kept below C., throughout the reaction. The product was kept nearlycompletely from insolubilization. A vary light colored fluid wasobtained. On adding 15 parts xylene, only 2 g. solid, incoherentparticles were found on filtering. The solution remained stable onstanding for three days.

3. 20 g. of the reaction productof Example 1(w-3) were used. 6.5 g.vinyl polysiloxane solution and 0.5 g. cumene hydroperoxide were added,and the vessel held between 65 C. and 85 C. At this low temperature, nocomplete 19 reaction was reached, and some jelly siloxanc remained atthe bottom of the vessel.

The preceding three reactions show that vinylpolysiloxane follows theprocess of this invention and that later secondary reactions of thevinyl group can be utilized. This is also demonstrated by Example 1(m).

(n) 23 parts of the reaction product of Example 1(y-2) were compoundedwith 10 parts of methyl phenyl silicone resin solution, commercialGeneral Electric 81132 (60% solution), and a jelly mass was obtained onmixing. 1.5 parts butyl titanate and 1 part tertiary-butyl perbenzoatewere added, and the mass was heated up to 185 C. A uniform melt wasobtained and dissolved in 25 parts toluene. On filtering, only 0.? partjelly substance remained on the filter cloth. After cooling, thesolution developed a slightly waxy cloud.

Example 6.--Compounding an alkyl titanate with a silicone resin and apolyhydric fatty acid ester Commercial silicone resins generally are notmiscible with oils, but they can be co-reacted in the presence of alkyltitanates and free oxygenreleasing organoperoxides in accordance withthe present invention.

(a) 20.5 parts silicone resin (DC 801, 60% solution) were slowly heatedto drive off the solvent. 9.2 parts soybean oil were added along withparts butyl titanate and 2 parts ditertiary-butyl peroxide. The mixturewas not uniformly miscible. On heeating, a slight gas development beganaround 85 C. and the components began to mix. At around 110 C., uniformliquid compound was obtained which was clearly soluble (1:07) in zenzol.This solution remained clear on cooling. A sample was spread over aglass plate, and no cloudiness was observed. It baked into a clear, hardcoating on the glass at around 110 C.

(b) 22 parts silicone resin (DC 801, 60% solution) were mixed with partstetra-cyclohexyl titanate and 14 parts China woodoil. 4 parts oftertiary-butyl perbenzoate were used. The mixture was not uniform andthe materials were not compatible. On heating, a heavy reaction occurredaround 150 C., and heating was continued up to about 185 C. On cooling,a heavy uniform compound was obtained having the appearance of a softresin. 8 g. was lost in the form of solvent from the silicone solutionand volatiles of the per compound. The new resin reaction prodnot wassoluble in coal tar solvents and dissolved in 39 parts xylene. Whenapplied to a steel panel and exposed to a temperature of about 100 C., acontinuous film was obtained within 90 minutes. The solution wasmiscible with the solution of the compounds produced in Example lih),Example 2(c) and Example 4(e) (c) parts silicone resin (DC 996) solids,were mixed with 9 parts tetra-cyclohexanol titanate and 10 parts of anon-drying vegetable oil, teaseed oil. 2 parts di-tertiary-butylperoxide were used. A clear, soluble compound was obtained on heatingthe mixture to 165 C. A 1:1 solution in toluene was light in color. Thissolution remained clear on standing for 60 hours. It was further diluted(1:1) with xylene, and this diluted solution was again mixed (1:1) withbutyl titanate. No precipitation occurred. The (1:1) solution of the newcompound in solvent was mixed (2:1) with liquid cobalt octoate drier and1 part VMP naphtha solvent was added. The solution remained clear.

As a medium for further modification, the (1:1) solution of the compoundin solvent was mixed (1:1) with ethyl tri-ethoxy silane, and a clearsolution was obtained. This was miscible (3:1) with soybean oil.

(d) 10 parts thermoplastic silicone resin (General Electric 9989-1) weremixed with 10 parts soybean oil and 10 parts butyl titanate. 2.8 partsof organic liquid hydroperoxide (Uniperox 60) were used. The mixture wasnot uniform. On heating, strong foaming occurred, especially around 150C. to 160 C. Heating was discontinued at around 192 C. 6 parts volatilesubstance had evaporated. The compound was clearly soluble in a mixtureof 10 parts xylene and 20 parts VMP naphtha solvent. This solution wascompatible on mixing with equal parts by volume of butyl titanate andethyl tri-ethoxy silane and mixtures thereof, as a base for furthermodification.

(e) 11.5 parts of a semi-drying vegetable oil, perilla oil, were mixedwith 21.5 parts silicone resin solution (DC 801, 50% solution). Neitherwas compatible and a slight gel was formed. 10 parts tetra-isopropyltitanate were added and mixed, but were not compatible. 2 parts benzoylperoxide with 5% stearic acid were added and the mixture was heated.Around 0., gas formation was observed. Heating was discontinued ataround 145 C. when a drop of the compound on a glass plate gave auniform clear mass. 6 g. volatile matter had escaped. 30 parts toluenewere added, and a clear solution was obtained which remained clear onstanding several hours. This solution dried on a glass plate overnightat 100 G. into a dry, transparent film.

(f) One volume silicone resin (General Electric 81132, 60% solution incoal tar solvent) was mixed with one volume synthetic drying oil(Isoline G-H, Woburn Chemical). The silicone was precipitated.

1. 21.5 g. silicone resin (General Electric 81132, 60% solution) weremixed with 10 g. of the same synthetic drying oil and with 12 g. butyltitanate. 2 g. lauroyl peroxide were added. On mixing, a non-uniformcondition was obtained, including a strong insoluble gel. On heating to100 C., the peroxide began to react under gas formation. Heating wascontinued under stirring. Around C. to C., the mass turned into auniform melt. Heating was continued to about C. 8 parts volatile matterhad escaped. The material was thinned with 23 parts toluene and a veryclear, light colored, slightly yellowish and reddish, stable solutionwas obtained. It was fully transparent and free of cloudiness.

(g) 5 parts phenol titanate were melted slowly with 4.5 parts of asemi-drying oil, soybean oil. A non-uniform solution was obtained as acloudy suspension. 4 parts commercial silicone resin (DC 803, 50%) wereadded, along with 1 part tertiary-butyl hydroperoxide. Around 110 C., astrong roaming occurred, and a dark melt was observed with a floatinggel. On further heating around 200 C. to 240 C., nearly all the jellymass had melted and was dissolved in 10 parts xylene. On filtering,around 0.5 g. residue was found. The remaining material was dissolvedand a stable, dark reddish-brown solution was obtained.

(h) 11 parts natural beeswax were melted and mixed with 10 parts butyltitanate and 11 parts of 60% methyl phenyl silicone resin solution (DC801) were added. As organoperoxide, 2 parts di-tertiary-butyl peroxidewere added. On heating, a fully uniform melt was obtained between.drier, and dissolved (Rezyl 99-5, 60% solids), an alkyd based upon alphthalic anhydride content of 43% and using a 110 C. and 140 C. Thiswas dissolved in 20 parts toluene, and nothing remained on the filtercloth. On standing, at room temperature, the solution formed a slightwaxy cloudy appearance.

(1') 11 parts of a synthetic wax-like liquid matter, polyethylene glycol400 di-tri-ricinoleate, were mixed with 11 parts butyl titanate and 12parts cyclo-hexenyl polysiloxane solution (Linde X-32). Asorganoperoxide, 2.5 parts tertiarybutyl hydroperoxide were added. Strongreaction occurred between 110 C. and 115 C., and 7 parts volatile matterescaped. The compound was dissolved (1:1) in toluene without residue anda very light colored and clear warm solution was obtained which remainedclear on standing for five hours at room temperature.

Example 7.Modifying compounds prepared.

from alleyl titanate with polyhydrz'c alcohol fatty acid esters and/orsilicone resins.

In a number of examples given throughout the specification, it has beenshown that the inbe modified further by adding more of the new compoundsor by increasing the alkyl titanate content.

(a) The reaction product of Example 1(e) was applied to a glass plateand baked at room temperature. It reached a Sward Hardness of 24 in twodays, at 20 C. When baked at 110 C. for two days, its Sward Hardness at20 C. was 40, and it did not become soft or tacky when covered withtransformer oil for 2 hours at 110 C.

The reaction product of Example 1(d) had a Sward Hardness of 26 whenbaked at 110 C., indicating good drying characteristics. A coatingthereof on tin plate showed a tendency to form fine cracks when observedunder the microscope, indicating a need for greater coherence.Modification thereof was accomplished as follows:

1. 10 parts in 50% solution were mixed with parts Chinawood oil, appliedto tinned sheet metal and baked at 100 C. for 2 hours. Dry coatings wereobtained. On ageing for 14 hours at 100 0., the films had a SwardHardness of 20 and did not show any tendency to crack. The solutionremained stable under observation for several days.

2. A plasticizer was used in the compound prepared in Example 1(0l) asfollows:

11 parts of the compound in 50% solution Were mixed with 4.5 partstricresylphosphate and a stable solution was obtained. This film, inview of the very high amount of plasticizer used for determining thecompatibility, had a Sward Hardness of 4.

3. parts of the solution of Example 1(d) with 50% solids were mixed witha commercial alkyd resin of the soya oil modified type having 50% solids(Rezyl 310-5). The materials produced, on baking on the same sheet metalunder the same curing conditions, a Sward Hardness of 18.

The reaction product of Example 1(z') was mixed with China-wood oil anda naphthenate (10:17) in alkyd resin Very fine state.

22 modifying oil of the non-drying oil type. 10 parts xylene were addedas diluent. On warming the mixture, a clear, stable solution wasobtained. On mixing similar portions of the same alkyd resin togetherwith the initial oil and xylene, no clear solution was obtainable.

4. The reaction product of Example 6(0) was modified with ethyltri-ethoxy silane and soybean oil was added to the solution. Similarly,liquid drier was substituted for the organosilane. Similar solutionswere made up with the reaction product of Example 6(d) and additionalalkyl titanate was added as a modifier. Similarly, the reaction productof Example 4(9) was modified with amyl tri-ethoxy silane and also withadditional alkyl titanate. Likewise, the compound of Example 1(l) wasmixed with ethyl trichloro silane.

In the processes set forth in Example 7, the alkyl titanates are used ina non-hydrolyzed form. If hydrolyzation occurs (caused by the use ofhydrogen peroxide), a portion of the reaction product is transformedinto an insoluble mass which cannot be resolubilized with metal soaps.Accordingly, the present specification and the appended claimsspecifically exclude hydrogen peroxide, an inorganic peroxide, from thefree oxygen-yielding compounds which are useful in the practice of thepresent invention.

Example 8.Efiect-of urea hydrogen peroxide on methyl titanate Methyltitanate is a white, granular solid material without a practical degreeof solubility in oils, toluene, cyclohexanol, methyl isobutyl ketone,isopropenyl acetate, etc. Methyl alcohol aifects it sufficiently topermit the particles to powder to fine size, but no clear solution isobtainable.

(a) 2 parts of methyl titanate were mixed with 3 parts of castor oilWetted with 2 parts methyl alcohol. 1.2 g. urea peroxide were added, andat C. a yellow reaction product appeared and the methyl titanategranular particles fell into a Complete liquefaction did not occur, anda fine yellow sedimentation began to appear. 0.5 part urea peroxide wasadded and the temperature was increased to C. 2 parts of castor oil wereadded to complete the reaction. A yellow substance was formed, but thefine sedi: mentation remained. In spite of the fact that castor oil issoluble in toluene, the reaction prodnot was taken up in toluene,filtered and the clear toluene solution was allowed to evaporate, a waxyproduct being obtained.

(1)) 2 parts of butyl titanate were used and the same kind ofsedimentation was formed in this case with urea peroxide, in spite ofthe fact that butyl titanate is much more resistant to decompositionthan methyl titanate in contact with moisture.

Example 9.E fiect of organoperorides on methyl titanate In order toproduce a more uniform area for inter-reaction, the following methodswere used to establish that the methyl titanate reacts with the oil inthe presence of organoperoxide.

(a) 5 parts methyl titanate were wetted with ensures volatile-matter hadescaped. sincezno clear melt had been obtained, parts commercial leadoctoate liquid (24% Pb), a metal soap, were added and heating continued.The product turned solid around 165" C. and was insoluble in toluene.

(b) The test was repeated, using 3 parts methyl .titanate, 6 partsmethyl alcohol, 9 parts bodied linseed oil (Z '2) and 1.2 partstertiary-butyl perbenzoate. The test proceeded in the same way. At 140C., 3.5 parts lead octoate liquid were added. At 170 C., a solid yellowto locally slight brown mass was obtained, which showed a'greater degreeof coherence than the product of the preceding Example (a).

(c) In order to retard the co-reaction further, -3 :partsmethyl titanatewere ground with 8 parts trieresylphosphate and 7 parts of bodiedlinseed .oil'were'added. After grinding, 2 parts tertiarybutylhydroperoxide were added. Around 130 C., violent reaction occurred,although the vessel had-been removed'from the heat source at around 120C. vA solid reaction product was obtained.

Example 10.Se1oaratton of a waxy reaction product of methyl titanate andpolyhydric alcoho! fatty acid esters with organoperori-des by separationof the soluble portion from the insoluble hydrolyzation product.

(a) 6 g. methyl titanate were mixed with 5 g. castor oil and moistenedwith 3 g. methyl alcohol. The titanate was broken up into a powder inthe fluids. 1 g. lauroyl peroxide was added and the mixture was slowlyheated. A reaction occurred around 75 C., whereby a yellowish-browncolor appeared. An incomplete melt was obtained and in 1:1 toluenesolution, a colored solution was obtained above a cloudy settled layer.

The same test was repeated using cumene hydroperoxide and thinning witha 1:1 mixture of methyl alcohol and toluene. Aiter evaporating thisvolatile matter, a waxy mass was obtained.

(17) 10 g. methyl titanate were mixed with 12 g. of a 45% toluenesolution of Llndes Silicone 39-32, a cyclohexenyl polysiloxane. 2 g.cumene 'hydroperoxide were added. On heating, a yellowish-brown colorappeared. Partial melting occurred, but a fine sediment was formed. Theproduct was thinned with 10 g. xylene and separated by filtering. Thesolution was allowed to evaporate and a waxy mass was obtained.

(c) The test of (b) above was repeated, using Lindes Silicone X-3l, avinyl polysiloxane, 50% in toluene. A strong reaction occurred onheating, and a black, mostly solid matter was formed.

(d) The attempt was made to eliminate partial hydrolysis by firstheating a mixture of 18g. linseed oil Z-2) and 0.5 g. cumenehydroperoxide to 70 C. and then adding 0.5 g. finely powdered methyltitanate and heating up to 180 C. A strong reaction occurred,-and a finepowder in yellowish-brown color was observed.

(6) Mixtures of methyl titanate and butyl titanate were tried also withsoybean oil and butyl perbenzoate, but full elimination of thesedimentation was not accomplished.

'lfihus, Example 10 illustrates that methyl titanate will co-react withpolyhydric alcohol fatty acid esters or silicones, or mixtures thereof,but it is not possible to avoid partial hydrolysis of the reactionproduct.

Accordingly, it will be apparent that the present invention makespossible the production of new and useful reaction products havingparproofing agents, etc.

24 'ticular value as film forming materials, water- Further, the presentinvention makespossible the compounding, formulating and application ofimpregnations, resin coatings, varnishes, paints, etc. The presentcompounds are highly heat-resistant but are easily curedand'aresurprisingly more-compatible with other coating compounds than are theconventional silicone resins. It will be apparent that furthermodifications and departures may be made by those :skilled in the art,and it is intendedthat all such variations be included as coming witinthe spirit and scope of the appended claims.

I claim as my invention:

1. A compositionof matter comprising the're action product or" an esterof titanic acid, and organic compound selected from the .groupconsisting-of esters of polyhydric alcohols with fatty acids having from10 to 31 carbon atoms and nionovalent hy rocarbcn poly-siloxane resins,said reactants being reacted in the presence of an organoperoxide at atemperature sufiicient to effect the release of free oxygen therein,said reaction product being soluble in coal-tar solvents and capable offorming a stable solution.

2. A composition of matter comprising the reaction product of an esterof titanic acid, and an ester or" a polyhydric alcohol with a fattyhaving from '10 to 31 carbon atoms, said reactants being reacted in thepresence of an organoperoxide at a temperature sufiicient to effect therelease of free oxygen therein, said reaction product being soluble incoal-tar solvents and capable of forming a stable solution therein.

3. A composition of matter comprising the reaction product of an esterof titanic acid, and a inoncvalent hydrocarbon poly-siloxane resin, saidreactants being reacted in the presence of an organopercxide at atemperature suiilcient to effect the release of free oxygen therein,said reaction product being soluble in coal-tar solvents and capable offorming a stable solution.

a. The composition set forth in claim 1 wherein the ester of titanicacid comprises butyl "'tanate.

5. The composition set forth in claim.2 wherein the fatty acid ester of.a polyhydric alcohol coin-p 'ises linseed oil.

6. The composition of claim 3 wherein the poly-siloxane resin comprisesmethyl phenyl poly-siloxane resin.

'3. The composition of claim 1 wherein the organoperoxide comprisesdi-tertiary-butyl per- Oxidev 8. A process for the preparation oforgano- "ta-hate reaction products which comprises reacting an ester oftitanic acid with an organic compound selectedfrom the group consistingof esters of poiyhydric alcohols with fatty acids having from 10 toill-carbon atoms and monovalent hydrocarbon poly-siloxane resins in thepresence of an organoperoxide at a temperature suflicient to efiect therel-ease of free oxygen therein to obtain organotitanate reactionproducts which are soluble in coal-tar solvents and capable of forming astable solution.

9. A process for the preparation of organetitanate reaction productswhich comprises reacting an ester of titanic acid with an ester of apolyhydric alcohol with a fatty acid having to effect the release offree oxygen therein to obtain organotitanate reaction products which aresoluble in coal-tar solvents and capable of forming a stable solution.

10. The process set forth in claim 9 wherein the ester of titanic acidcomprises butyl titanate.

11. The process set forth in claim 9 wherein the fatty acid ester ofpolyhydric alcohol comprises linseed oil.

12. The process set forth in claim 9 wherein the organoperoxidecomprises di-tertiary-butyl peroxide.

13. A process for the preparation of organotitanate reaction productswhich comprises re acting an ester of titanic acid with a monovalenthydrocarbon poly-siloxane resin in the presence of an organoperoxide ata temperature sufficient to effect the release of free oxygen therein toobtain organotitanate reaction products which are soluble in coal-tarsolvents and capable of forming a stable solution.

14. The process set forth in claim 13 wherein the ester of titanic acidcomprises butyl titanate.

15. The process set forth in claim 13 wherein the poly-siloxane resincomprises methyl phenyl poly-siloxane resin.

16. The process is set forth in claim 13 wherein the organoperoxidecomprises di-tertiary-butyl peroxide.

17. A process for the preparation of organotitanate reaction productswhich comprises reacting an ester of titanic acid with an ester of apolyhydric alcohol with a fatty acid having from to 31 carbon atoms anda monovalent hydrocarbon poly-siloxane resin in the presence of anorganoperoxide at a temperature sufficient to effect the release of freeoxygen therein to obtain organotitanate reaction products which aresoluble in coal-tar solvents and capable of forming a stable solution.

18. A composition of matter comprising the reaction product of an esterof titanic acid, an ester of a polyhydric alcohol with a fatty acidhaving from 10 to 31 carbon atoms and a monovalent hydrocarbonpoly-siloxane resin, said reactants being reacted in the presence of anorganoperoxide at a temperature suificient to effect the release of freeoxygen therein, said reaction product being soluble in coal-tar solventsand capable of forming a stable solution.

19. A composition of matter comprising the reaction product of butyltitanate, soyabean oil, and methyl phenyl polysiloxane resin, saidreactants being reacted in the presence of ditertiary-butyl peroxide ata temperature sufficient to effect the release of free oxygen therein,said reaction product being soluble in coal-tar solvents and capable offorming a stable solution therein.

20. The composition of matter set forth in claim 1 wherein the amount oforganoperoxide comprises from about 1 to 25 per cent by weight of thenon-volatiles.

21. The process set forth in claim 8 wherein the amount oforganoperoxide comprises from about 1 to 25 per cent by weight of thenonvolatiles.

22. The process set forth in claim 17 wherein the amount oforganoperoxide comprises from about 6 to 23 per cent by weight of thenonvolatiles.

23. The process set forth in claim 9 wherein the amount oforganoperoxide comprises from about 2.4 to 20 per cent by weight of thenonvolatiles.

24. The process set forth in claim 13 wherein the amount oforganoperoxide comprises from about 1.6 to 13.5 per cent by weight ofthe nonvolatiles.

25. The process set forth in claim 8 wherein the reacting temperature isfrom about to 220 C.

26. A process for the preparation of organotitanate reaction productswhich comprises reacting an ester of titanic acid with an organiccompound selected from the group consisting of esters of polyhydricalcohols with fattyacids having from 10 to 31 carbon atoms andmonovalent hydrocarbon poly-siloxane resins in the presence of anorganoperoxide at a temperature from about 90 to C'. sufiicient toeffect the release of free oxygen therein and thereafter continuing thereaction at a temperature from about to 220 C. to obtain organotitanatereaction products which are soluble in coal-tar solvents and capable offorming a stable solution.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,512,058 Gulledge June 20, 1950 2,620,318 Boyd et a1. Dec. 2,1952 OTHER REFERENCES Kraitzer et al., J. Oil & Colour Chemists Assn.31, No. 340, pages 405-417 (1948).

1. A COMPOSITION OF MATTER COMPRISING THE REACTION PRODUCT OF AN ESTEROF TITANIC ACID, AND AN ORGANIC COMPOUND SELECTED FROM THE GROUPCONSISTING OF ESTERS OF POLYHYDRIC ALCOHOLS WITH FATTY ACIDS HAVING FROM10 TO 31 CARBON ATOMS AND MONOVALENT HYDROCARBON POLY-SILOXANE RESINS,SAID REACTANTS BEING REACTED IN THE PRESENCE OF AN ORGANOPEROXIDE AT ATEMPERATURE SUFFICIENT OF EFFECT THE RELEASE OF FREE OXYGEN THEREIN,SAID REACTION PRODUCT BEING SOLUBLE IN COAL-TAR SOLVENTS AND CAPABLE OFFORMING A STABLE SOLUTION.